CRYSTAL

GROWTH
Seed-Mediated Growth of Nearly Monodisperse Palladium & DESIGN
Nanocubes with Controllable Sizes
2008
Wenxin Niu,†,‡ Zhi-Yuan Li,§ Lihong Shi,†,‡ Xiaoqing Liu,†,‡ Haijuan Li,†,‡ Shuang Han,†,‡ VOL. 8, NO. 12
Jiuan Chen,†,‡ and Guobao Xu*,† 4440–4444
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry,
Chinese Academy of Sciences, Changchun 130022, China, Graduate UniVersity of the Chinese
Academy of Sciences, and Institute of Physics, Chinese Academy of Sciences, Beijing 100080, China

ReceiVed March 4, 2008; ReVised Manuscript ReceiVed May 6, 2008

ABSTRACT: Nearly monodisperse Pd nanocubes with controllable sizes were synthesized through a seed-mediated growth approach.
By using Pd nanocubes of 22 nm in size as seeds, the morphology of the as-grown nanostructures was fixed as single-crystalline,
which enabled us to rationally tune the size of Pd nanocubes. The formation mechanism of initial 22 nm nanocubes was also
discussed. The size-dependent surface plasmon resonance properties of the as-synthesized Pd nanocubes were investigated. Compared
with previous methods, the yield, monodispersity, perfection of the shape formation, and the range of size control of these nanocubes
are all improved. These Pd nanocubes may have potential interests in surface-enhanced Raman scattering, sensors, catalysis, study
of size-dependent properties, and fabrication of high-order structures.

Introduction Sinopharm Chemical Reagent Co., Ltd. (China). Cetyltrimethylammo-

Metallic nanoparticles show many properties that are signifi-
cantly different from those of their bulk counterparts.1 To study
their size- and shape-dependent properties, considerable attention
has been paid to developing new synthetic methods,2,3 and
significant progress has been made while many subjects remain
unexplored. Palladium, well-known for its high hydrogen
solubility4 and effective catalytic activity5 for Stille, Heck, and
Suzuki reactions, has received much attention in recent research
of shape-controlled synthesis of metallic nanostructures. Various
Pd nanostructures have been synthesized;6 a polyol process7 and
a water-based synthesis developed recently8 have been proven
to be very versatile methods. Pd nanocubes have been synthe-
sized through several methods;9-12 however, most of these
methods still need improvement in terms of yield, monodis-
persity, perfection of cube formation, and size control. In this
study, we report a facile process to prepare small Pd nanocubes
of 22 nm in size with a high yield of 95.5%. Using the as-
synthesized small Pd nanocubes as seeds, nearly monodisperse
Pd nanocubes with controllable sizes from 37 to 109 nm could
be obtained through a seed-mediated growth approach. Com-
pared with previous methods, the yield, monodispersity, perfec-
tion of the shape formation, and the range of size control of
these nanocubes are all improved. The formation mechanisms
of the Pd nanocubes were investigated and discussed. The
surface plasmon resonance (SPR) properties of Pd nanocubes
were investigated and compared with theoretical calculations
using the discrete dipole approximation (DDA).
Experimental Section
Chemicals and Materials. Cetyltrimethylammonium bromide (CTAB,
99.0%) was obtained from Shanghai Sagon Company (China). L-
Ascorbic acid (99.7%) was obtained from Beijing Chemical Reagent
Company (China). Sodium borohydride (NaBH4, 96%) and palla-
dium(II) chloride (PdCl2, anhydrous, 59% as Pd) were obtained from
* Author to whom correspondence should be addressed. E-mail: guobaoxu@
ciac.jl.cn. Tel: +86-431-85262747. Fax: +86-431-85262747.
†
Changchun Institute of Applied Chemistry.
‡
Graduate University of the Chinese Academy of Sciences.
§
Institute of Physics, Chinese Academy of Sciences.
nium chloride (CTAC, 98.0%) was obtained from Tianjin Guangfu Fine
Chemical Research Institute (China). All the chemicals were analytical
grade reagents and used without further purification. Double distilled
water was used throughout the experiments. A ten millimolar H2PdCl4
solution was prepared by dissolving 0.1773 g of PdCl2 in 10 mL of
0.2 M HCl and further diluting to 100 mL with double distilled water.
Synthesis of 22 nm Pd Nanocubes. 0.5 mL of 10 mM H2PdCl4
solution was added to 10 mL of 12.5 mM CTAB solution under stirring,
and then the solution was heated at 95 °C for 5 min before 80 µL of
freshly prepared 100 mM ascorbic acid solution was added. The reaction
was allowed to proceed for 30 min.
Seed-Mediated Growth of Bigger Pd Nanocubes. 125 µL of 10
mM H2PdCl4 solution was added to 5 mL of 50 mM CTAB solution
kept at 40 °C, different volumes (400 µL for 37 nm, 200 µL for 44
nm, 80 µL for 56 nm, 40 µL for 76 nm, 10 µL for 109 nm nanocubes)
of the as-synthesized 22 nm Pd nanocubes solution were added, and
then 25 µL of freshly prepared 100 mM ascorbic acid solution was
added and mixed thoroughly. The resulting solution was placed in a
water bath at 40 °C. The reactions were stopped after 14 h by
centrifuging (12000 rpm, 10 min). The precipitates were redispersed
in deionized water for UV-visible extinction spectra characterization.
Two more centrifugations (12 000 rpm, 10 min) were applied to the
samples for scanning electron microscopy (SEM) and transmission
electron microscopy (TEM) characterization.
Control Experiments. (a) One-step synthesis of Pd nanoparticles
(CTAC-capped Pd seeds) in the presence of CTAC. All procedures were
the same as those described for synthesis of 22 nm Pd nanocubes except
that CTAC was used instead of CTAB. (b) Seed-mediated growth of
bigger Pd nanoparticles with CTAC-capped Pd seeds in CTAB solution.
All procedures were the same as those described for seed-mediated
growth of bigger Pd nanocubes except that 80 µL of CTAC-capped
Pd seed solution was added as seeds. (c) Seed-mediated growth of bigger
Pd nanoparticles with CTAC-capped Pd nanoparticle as seeds in CTAC
solution All procedures were the same as those described for seed-
mediated growth of bigger Pd nanocubes except that 80 µL of CTAC-
capped Pd seed solution was added as seeds and CTAC solution was
used instead of CTAB solution. (d) Seed-mediated growth of bigger
Pd nanoparticles with smaller Pd nanoparticles of 3-4 nm in size as
seeds. All procedures were the same as those described for seed-
mediated growth of bigger Pd nanocubes except that 2.5 µL of smaller
Pd nanoparticle solution was added as seeds.
Instrumentation. TEM studies were performed with a HITACHI
H-8100 TEM operated at 200 kV. SEM images were taken using a
FEI XL30 ESEM FEG scanning electron microscope operating at 25
kV. Selected area electron diffraction studies were performed on a
Tecnai G2 20 S-TWIN TEM operated at 200 kV. At least 100 nanocubes

10.1021/cg8002433 CCC: $40.75  2008 American Chemical Society

Published on Web 09/25/2008
Growth of Nearly Monodisperse Pd Nanocubes
Figure 1. (a) SEM image of initial small Pd nanocubes of 22 nm in
size. The inset shows corresponding TEM image (scale bar: 100 nm).
(b-f) SEM images of 37 nm, 44 nm, 56 nm, 76 nm, and 109 nm Pd
nanocubes (scale bar: 200 nm).
were measured for size distribution. UV/vis extinction spectra were
taken at room temperature on a CARY 500 Scan UV/vis/near IR
spectrophotometer using a quartz cuvette with an optical path of 1 cm.
X-ray diffraction measurements were obtained with a Philips PW1710
X-ray diffractometer (Cu KR radiation).
Results and Discussion
Initial small Pd nanocubes were synthesized through a one-
step reduction of H2PdCl4 with ascorbic acid in 12.5 mM CTAB
aqueous solution at 95 °C. The reduction process was rather
fast and the color of the solution turned brownish yellow within
30 s. The reaction was allowed to proceed for 30 min. Figure
1a shows SEM and TEM images of these nanocubes. The yield
for these nanocubes was 95.5%, and byproducts included
polyhedral (3.8%) and rodlike (0.6%) nanoparticles. The average
size and size distribution of these nanocubes are 22 nm and
3.6%, respectively. A corresponding histogram of size distribu-
tion is shown in Figure S1a, Supporting Information.
To grow bigger Pd nanocubes, a seed-mediated growth
approach was adopted using the as-synthesized 22 nm nanocubes
as seeds. A seed-mediated growth approach separates the
nucleation and growth stages of nanoparticles, which provides
better control over the size, size distribution, and shape evolution
of nanoparticles.3 It has been reported that the growth of Pd
nanoparticles could proceed in a controlled manner at relatively
low temperatures.11,13,14 Therefore, our growth reactions were
performed at 40 °C in 50 mM CTAB solution with ascorbic
acid as reductant, and were stopped by centrifugation after 14 h.
The final edge length of nanocubes could be tuned by adding
different volumes of seed solution. Figure 1b-f shows SEM
images of five batches of the enlarged nanocubes obtained by
adding different volumes of seed solutions. By comparison, the
Crystal Growth & Design, Vol. 8, No. 12, 2008 4441
Figure 2. SEM image of the assembly of 56 nm Pd nanocubes (scale
bar: 1 µm).
Figure 3. TEM images and corresponding SAED patterns of (a, b) a
single seed Pd nanocube and (c, d) a single seed-mediated grown Pd
nanocube (scale bar: 20 nm).
volume increment of a single Pd nanocube increased about 36
times as the volumes of the added seed solution decreased from
400 to 10 µL. Figure S1b-f, Supporting Information shows
histograms of size distributions for the five batches of nanocubes.
Table S1, Supporting Information shows corresponding average
sizes, size distributions, yields, and byproducts of the nanocubes.
The average sizes (size distributions) of the five batches of
nanocubes are 37 nm (3.7%), 44 nm (4.4%), 56 nm (5.0%), 76
nm (7.1%), and 109 nm (7.0%), respectively. The yields for
the five batches of nanocubes are 92.4%, 90.2%, 93.3%, 75.2%,
and 70.6%, respectively. 37, 44, 56, and 76 nm Pd nanocubes
shared the features of nearly perfect sharp corners and edges,
while 109 nm Pd nanocubes were slightly truncated. Some of
these nanocubes could assemble into large-scale ordered two-
dimensional arrays on the ITO substrates (Figure 2), which also
demonstrated their monodispersity. In accordance with previous
reports, residual CTAB was found to be essential for the
formation of ordered assembly.2g,12 If the sample was washed
three times (once more than the normal procedure), ordered
assembly of the nanocubes could not form (Figure S2, Sup-
porting Information). However, the residual CTAB could affect
the quality of the SEM images; therefore, Figure S2, Supporting
Information are slightly clearer than Figure 1.
Figure 3 shows TEM images and corresponding selected area
electron diffraction (SAED) patterns of a single seed Pd
nanocube and a single seed-mediated grown Pd nanocube. The
square spot arrays of SAED patterns show that they both are
4442 Crystal Growth & Design, Vol. 8, No. 12, 2008
Figure 4. UV/vis extinction spectra of Pd nanocubes of different sizes:
(a) 22 nm; (b) 37 nm; (c) 44 nm; (d) 56 nm; (e) 76 nm; (f) 109 nm (all
spectra are normalized against the intensities of their main adsorption
peaks).
single crystals bound by {100} facets; such SAED patterns have
been observed in the case of silver and gold nanocubes.15 The
X-ray diffraction (XRD) pattern of Pd nanocubes of ∼50 nm
in size has an abnormally intense (200) peak (Figure S3,
Supporting Information), which suggests that most of the Pd
nanocubes were preferentially oriented with their {100} facets
parallel to the substrate.
Size control is an efficient method to tune the SPR properties
of Pd nanocubes.9 Here we investigated these properties in a
broader size range. Figure 4 shows that the SPR peaks of Pd
nanocubes progressively shift from 290 to 580 nm as the sizes
of Pd nanocubes increase from 37 to 109 nm. In contrast to
smaller ones, the SPR properties of 109 nm nanocubes showed
some new features. The extinction peak became extremely
broad, and a shoulder peak appeared at about 400-450 nm.
Theoretical extinction cross-section curves of a Pd nanocube
of 109 nm calculated using DDA16,2c are displayed in Figure
5b. The location of the calculated peaks roughly matches with
the experimentally measured spectrum shown in Figure 5a. We
consider that the deviation is due to a relatively low yield
(70.6%) for 109 nm Pd nanocubes. Moreover, truncation of 109
nm Pd nanocubes may also lead to a blue-shift of the SPR
bands.17 According to the DDA calculations, we can also
identify that the shoulder peak of experimentally measured
spectrum is from adsorption while the main peak is an overlap
of scattering and adsorption. Moreover, 109 nm Pd nanocubes
show strong scattering properties compared with 50 nm ones
reported previously.9
Two considerations were taken into account to understand
the formation mechanisms of Pd nanocubes, that is, why the
nanocrystals were formed as single crystals and why the
nanocrystals were formed bound by {100} facets.
In the case of growth of 22 nm Pd nanocubes, controlled
experiments were carried out to understand why the nanocrystals
were formed as single crystals. We found the reaction became slow
when the concentration of CTAB was increased to 50 mM or 100
mM while keeping other parameters unchanged. The final products
were polydisperse nanoparticles (Figure S4a,b, Supporting Infor-
mation). Similar results were obtained when the reaction temper-
ature was decreased to 40 °C (Figure S4c, Supporting Information).
Therefore, relatively fast nucleation favors the formation of Pd
nanocubes.7,18 Fast growth may have reduced the time available
for the formation of twin defects,19 resulting in the formation of
single crystal Pd nanoparticles. Oxidative etching process has been
Niu et al.
Figure 5. (a) UV/vis extinction spectra of 109 nm Pd nanocubes. (b)
Extinction (Qext), scattering (Qsca), and absorption (Qabs) cross sections
calculated for a Pd nanocube with an edge length of 109 nm using the
DDA method (Qext ) Qabs + Qsca).
used to grow single-crystalline nanoparticles by selectively dis-
solving twinned nanoparticles with chloride or bromide in the
presence of oxygen.20 It may not be responsible for the formation
of single-crystalline Pd nanocubes herein for the following reasons:
(1) In oxidative etching process, Cl- is known to be more corrosive
than Br-;20c,21 therefore, it was supposed to get single-crystalline
nanoparticles in the presence of cetyltrimethylammonium chloride
(CTAC) if the reaction followed the oxidative etching mechanism.
However, if CTAB was replaced with CTAC, the final product
was a mixture of polydisperse nanoparticles of irregular shapes
(Figure S5a, Supporting Information). Seed-mediated growth of
larger Pd nanoparticles by using these CTAC-capped nanoparticles
as seeds in 50 mM CTAB solution also produced various
nanostructures, which suggests the nonuniformity of crystal
structures of the initial CTAC-capped seeds (Figure S5b, Support-
ing Information). (2) Oxygen is necessary in the oxidative etching
process.20 However, ascorbic acid is an oxygen scavenger22 and
has been used to prevent copper nanoparticles from being oxi-
dized.23 It may play the same role for Pd nanoparticles. (3)
Oxidative etching could be partially eliminated at low temperatures
such as 70 °C.18 However, we have obtained nanocubes in high
yields at temperatures as low as 65 °C (Figure S6, Supporting
Information).
In the seed-mediated growth procedure, the adoption of 22
nm Pd nanocubes as seeds was responsible for preservation of
the single-crystalline nature of the as-synthesized larger Pd
nanocubes. To demonstrate the importance of seeds, we prepared
smaller Pd nanoparticles of 3-4 nm according to Berhault et
al., 80% of these nanoparticles were supposed to be single-
crystalline.11 When these smaller Pd nanoparticles were used
as seeds, the product was a mixture of multiple shapes (Figure
S7, Supporting Information). This result suggests that the
Growth of Nearly Monodisperse Pd Nanocubes
utilization of large single-crystalline seeds was critical for the
formation of nanocubes in high yields in the seed-mediated
growth procedure. It is believed that crystal structure of seeds
fluctuates at very small sizes, but the structure will be fixed as
single-crystalline or multitwinned as the size of the crystal
increases.24 The size of the seeds used in our synthesis was
large enough to avoid twinning, which enabled us to rationally
tune the size of Pd nanocubes through the seed-mediated growth
procedure.
The as-synthesized Pd nanocubes are bound by {100} facets.
It has been reported that CTAB could preferentially bind to the
{100} crystal facets of palladium and promote the formation
of {100} facets of palladium.6g,13 In a control experiment CTAC
was used instead of CTAB in the whole seed preparation and
seed-mediated growth procedures; the as-synthesized nanopar-
ticles were polydisperse, and most of these nanoparticles had
rough surfaces (Figure S5c, Supporting Information). The
appearance of these irregular shapes implies that the presence
of bromide is essential for the formation of well-defined {100}
facets. A previous report has studied the adsorption of bromide
on the surface of Pd nanostructures in detail.21 Bromide was
found to be capable of chemisorbing onto the surface of
palladium seeds to promote the formation of {100} facets.
Compared with bromide, chloride cannot efficiently stabilize
and promoted the formation of {100} surfaces of Pd. Another
report also suggested that bromide ions from trimethyl(tetrade-
cyl)ammonium bromide effectively stabilize the {100} faces
of rhodium, platinum, and palladium.25 Both reports and the
control experiment with CTAC as surfactant suggest that Br-
from CTAB played an important role in the formation of
nanocubes with well-defined {100} surfaces.
Finally, we note that the ability of producing Pd nanocubes
larger than 109 nm by this seed-mediated growth procedure is
still limited. Unlike seed-mediated growth of gold and silver
nanostructures,3 catalytical growth of Pd on preformed seeds
is quite slow at 40 °C. If too few seeds were added to the growth
solution, spontaneous nucleation would occur because there were
too few deposition spots. In an experiment with only 1 µL of
seeds added, the initial seeds grew into large cuboctahedra of
160 nm in size while spontaneous nucleation resulted in the
formation of Pd nanorods, right bipyramids, and small nanocubes
(Figure S8a,b, Supporting Information). It is noteworthy that
Pd cubooctahedron are bound by {100} and {111} facets.20b,21
The formation of Pd cubooctahedron suggests that the growth
rate of Pd along <100> and <111> directions could be
modulated by adding different volumes of seed solution. Recent
reports also showed that Pd octahedral and icosahedra bound
by {111} facets could be synthesized in the presence of CTAB.11
These results suggest that finer shape control over the nanoc-
rystals may be achieved through selective stabilization of crystal
facets and growth kinetic modulation. However, spontaneous
nucleation added much complexity to the reaction; further
studies are still needed to fully understand the growth mecha-
nism of Pd cubooctahedron.
Conclusion
In conclusion, the seed-mediated growth approach was
demonstrated as an efficient method to synthesize nearly
monodisperse palladium nanocubes in high yields with broad
size control. By using 22 nm Pd nanocubes as seeds, twinning
was successfully avoided during the growth process. The size-
dependent surface plasmon resonance properties of the as-
synthesized Pd nanocubes were investigated. 109 nm Pd
nanocubes show strong scattering properties compared with 50
Crystal Growth & Design, Vol. 8, No. 12, 2008 4443
nm ones. These Pd nanocubes may have potential applications
in surface-enhanced Raman scattering, SPR sensors, catalysis,
and fabrication of high-order structures.
Acknowledgment. We gratefully acknowledge support from
the National Natural Science Foundation of China (No.
20505016), Department of Sciences & Technology of Jilin
Province (20070108), and Hundred Talents Program of Chinese
Academy of Sciences. Z.-Y.L. thanks the National Natural
Science Foundation of China (No. 10525419 and 60736041)
for financial support.
Supporting Information Available: XRD pattern of Pd nanocubes
of ∼50 nm, histograms of size distribution of Pd nanocubes of different
sizes, SEM images of Pd nanoparticles synthesized at different
conditions (Figures S1-S8), and size and shape distributions of Pd
nanocubes of different sizes (Table S1). This material is available free
of charge via the Internet at http://pubs.acs.org.
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CG8002433